Energy-curable cyanate/ethylenically unsaturated compositions

A composition of matter including a polymerizable mixture comprising 1 to 99 weight percent of a first monomer and an initiator therefor, the first monomer being one of 1) at least one free-radically polymerizable monomer or 2) at least one cyanate ester monomer, and 99 to 1 weight percent of a second monomer and an initiator therefor, the second monomer being the member of 1) or 2) that is not selected as the first monomer, wherein the curative for the cyanate ester is a transition metal-containing organometallic compound curing agent and the curative for the free-radically polymerizable monomer is a free-radical generating curing agent or a transition metal-containing organometallic compound. The polymeric mixtures are useful, for example, in applications requiring high performance, such as high temperature performance; in composites, particularly structural composites; structural adhesives; vibration damping materials; electronic applications such as printed wiring boards, semiconductor encapsulants and electronic adhesives; photoresists; injection molding and prepregs; protective coatings; tough self-supporting films; and high performance binders. In addition, a curable composition including (1) an ethylenically unsaturated monomer or (2) an ethylenically unsaturated monomer and a cyanate ester monomer, and certain organometallic neutral compounds is useful in the graphic arts.

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Claims

1. A composition of matter comprising a curable mixture comprising 1 to 99 weight percent of a first monomer and an initiator therefor, the first monomer being one of 1) at least one ethylenically unsaturated monomer or 2) at least one cyanate ester monomer, and 99 to 1 weight percent of a second monomer and an initiator therefor, the second monomer being the member of 1) or 2) that is not selected as the first monomer, wherein a curative for the cyanate ester is a transition metal-containing organometallic compound curing agent and a curative for the ethylenically unsaturated monomer is a free-radical generating curing agent or a transition metal-containing organometallic compound, said composition when one or more of said monomers has at least commenced curing comprises one or both of an interpenetrating polymer network and a semi-interpenetrating polymer network, said networks comprising a semi-phase separated morphology which includes a continuum of phase compositions.

2. The composition according to claim 1 wherein said ethylenically unsaturated monomer is selected from the group consisting of acrylates and methacrylate monomers.

3. The composition according to claim 1 wherein said cyanate ester monomer has the formula

4. The composition according to claim 3 further comprising at least one monofunctional cyanate compound of formula QOCN, wherein Q is as defined in claim 3.

5. The composition according to claim 1 wherein said organometallic compound has the formula

L.sup.1 represents none, or 1 to 12 ligands contributing pi-electrons that can be the same or different selected from the group consisting of a) acyclic unsaturated and cyclic unsaturated compounds and groups, b) carbocyclic aromatic compounds and groups, and c) heterocyclic aromatic compounds and groups, each capable of contributing 2 to 24 pi-electrons to file valence shell of M;
L.sup.2 represents none, or 1 to 24 ligands that can be the same or different contributing an even number of sigma-electrons that are selected from mono-, di-, and tri-dentate ligands, each donating 2, 4, or 6 sigma-electrons to the valence shell of M;
L.sup.3 represents none, or 1 to 12 ligands that can be the same or different, each contributing no more than one sigma-electron each to the valence shell of each M;
M represents 1 to 6 of the same or different racial atoms selected from the group consisting of the elements of Periodic Groups IVB, VB, VIB, VIIB, and VIII;
e is an integer having a value of 0, 1 or 2, such that the organometallic portion of the molecule is neutral, cationic or dicationic;
each X is selected from the group consisting of organic sulfonates, halogenated metals or metalloids, and alkylated or arylated metal or metalloid; and p-toluenesulfonate, p-chlorobenzenesulfonate, BF.sub.4.sup.-, PF.sub.6.sup.-, AsF.sub.6.sup.-, SbF.sub.6.sup.-, FeCl.sub.4.sup.-, SnCl.sub.5.sup.-, SbF.sub.5.sup.-, AlF.sub.6.sup.-, GaCl.sub.4.sup.31, InF.sub.4.sup.-, TiF.sub.6.sup.-, CH.sub.3 SO.sub.3.sup.-, B(C.sub.6 H.sub.5).sub.4.sup.-, C.sub.6 H.sub.5 SO.sub.3.sup.-, CF.sub.3 SO.sub.3.sup.-, SbF.sub.5 OH.sup.-, and SbCl.sub.6.sup.-;
f is an integer of 0, 1 or 2, the number of anions required to balance the charge e on the organometallic portion;
with the proviso that the organometallic compound contains at least one transition metal-carbon bond; and with tile proviso that L.sup.1, L.sup.2, L.sup.3, M, c, X, and f are chosen so as to achieve a stable configuration.

6. The composition according to claim 5 wherein X is a tetraalkyl or tetraaryl borate.

7. The composition according to claim 5 wherein X is selected from the group consisting of BF.sub.4.sup.-, PF.sub.6.sup.-, AsF.sub.6.sup.-, SbF.sub.6.sup.-, B(C.sub.6 H.sub.5).sub.4.sup.-, CF.sub.3 SO.sub.3.sup.-, and SbF.sub.5 OH.sup.-.

8. The composition according to claim 1 wherein said initiators are independently thermally or photochemically initiated in any combination and in any order to provide a polymeric mixture.

9. The composition according to claim 1 wherein said ethylenically unsaturated monomer is present in the range of 70 to 30 weight percent and said at least one cyanate ester monomer is present in the range of 30 to 70 weight percent.

10. The composition according to claim 1 wherein said ethylenically unsaturated monomer is present in the range of 60 to 40 weight percent and said at least one cyanate ester monomer is present in the range of 40 to 60 weight percent.

11. The polymeric mixture according to claim 8.

12. A process for providing a mixture of polymerized cyanate ester monomer and polymerized ethylenically unsaturated monomer comprising the steps of

a) providing a polymerizable admixture by adding in any order at least one cyanate ester monomer, at least one ethylenically unsaturated monomer, a catalytically effective amount of a cyanate ester curing agent comprising a transition metal-containing organometallic compound and a catalytically effective amount of a free-radical curing agent comprising an organic compound capable of generating free radicals, and
b) allowing the mixture to polymerize or adding energy to the mixture to effect polymerization so as to provide a composition comprising one or both of an interpenetrating polymer network and a semi-interpenetrating polymer network, said networks comprising a semi-phase separated morphology which includes a continuum of phase compositions.

13. The method according to claim 12 wherein said curing agents are activated by energy in a simultaneous manner or in a sequential manner.

14. The method according to claim 13 wherein said simultaneous or sequential activation of said catalyst is by at least one of heat and light.

15. The method according to claim 12 further comprising one or both of steps a) and b):

a) prepolymerizing at least one of said ethylenically unsaturated monomers to produce a syrup in which said monomer(s) has at least commenced polymerization, and
b) prepolymerizing at least one of said cyanate ester monomers to produce an oligomer in which said monomer(s) has at least commenced polymerization.

16. The method according to claim 12 wherein said admixture further comprises at least one bireactive crosslinking monomer.

17. The method according to claim 12 wherein said polymerization is controlled by at least one of rate of polymerization and diffusion of each component monomer to provide at least one of a phase separated or a phase mixed morphology.

18. A curable adhesive composition comprising an admixture comprising

1 to 99 weight percent of a first monomer and an initiator therefor, the first monomer being one of 1) at least one ethylenically unsaturated polymerizable monomer and 2) at least one cyanate ester monomer, and 99 to 1 weight percent of a second monomer and an initiator therefor, the second monomer being the member of 1) and 2) that is not selected as the first monomer, when the curing agent for said cyanate ester is a transition metal containing organometallic compound and the curing agent for said free-radically polymerizable monomer is a free-radical generating curing agent, said composition when at least partially cured comprising one or both of an interpenetrating polymer network and a semi-interpenetrating polymer network, said networks comprising a semi-phase separated morphology which includes a continuum of phase compositions.

19. The composition according to claim 18 wherein at least one of said ethylenically unsaturated monomers is polymerized prior to polymerization of said at least one cyanate ester monomer.

20. The composition according to claim 19 which is an electronic adhesive.

21. A curable composition comprising an admixture comprising

1 to 99 weight percent of a first monomer and an initiator therefor, the first monomer being one of 1) at least one free-radically polymerizable monomer and 2) at least one cyanate ester monomer, and 99 to 1 weight percent of a second monomer and an initiator therefor, the second monomer being the member of 1) and 2) that is not selected as the first monomer, wherein the curing agent for said cyanate ester is a transition metal containing organometallic compound and the curing agent for said free-radically polymerizable monomer is a free-radical generating curing agent, said curable composition being a photoresist, said composition when cured comprising one or both of an interpenetrating polymer network and a semi-interpenetrating polymer network, said networks comprising a semi-phase separated morphology which includes a continuum of phase compositions.

22. The cured composition according to claim 1.

23. The composition according to claim 5 wherein any of said L.sup.1 ligands are substituted by a species selected from the group consisting of alkyl, alkoxy, aryl, phenyl, halo, cyano, and nitro groups.

Referenced Cited
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4223073 September 16, 1980 Caldwell et al.
4383903 May 17, 1983 Ayano et al.
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4952612 August 28, 1990 Brown-Wensley et al.
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Foreign Patent Documents
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Other references
  • J.M.G. Cowie, "Comprehensive Polymer Science", G. Allen & J.C. Bevington, Eds., Pergamon Press, Oxford, 1989, vol. 3, pp. 1-15. Wagner & Purbrick, J. Photographic Sci., 1981, 29, 230-235. Bamford & Mullik, J. Chem. Soc. Faraday I, 1976, 72, 368-375. Bamford & Al-Lamee, J. Chem. Soc. Faraday I, 1984, 80, 2175-2186, 2187-2197 .
Patent History
Patent number: 5744557
Type: Grant
Filed: Jun 16, 1993
Date of Patent: Apr 28, 1998
Assignee: Minnesota Mining and Manufacturing Company (St. Paul, MN)
Inventors: Fred B. McCormick (Maplewood, MN), David J. Drath (Woodbury, MN), Ilya Gorodisher (Stillwater, MN), Michael A. Kropp (Cottage Grove, MN), Michael C. Palazzotto (St. Paul, MN), Melville R. V. Sahyun (Maplewood, MN)
Primary Examiner: Fred Zitomer
Attorneys: Lorraine R. Sherman, Philip Y. Dahl
Application Number: 8/78,981